Process for preparing copolymers

ABSTRACT

A catalyst comprising an organoaluminum compound, an organic halogen compound containing labile halogen atom, and a compound of metal of Groups IV B-VII B or Group VIII of Deming&#39;&#39;s Periodic table is useful for copolymerizing conjugated dienes, conjugated heterodienes and, if desired, monoolfins to produce an alternate copolymer.

United States Patent 1 Ichikawa et al.

[54] PROCESS FOR PREPARING COPOLYMERS [75] Inventors: Mitsuo Ichikawa; Yasumasa Takeuchi; Yoshiyuki Harita;

Masayuki Endo, all of Yokkaichi; Nobuo Yamaguchi, Mie; Mitsuru Tashiro; Akira Kogure, both of Yokkaichi, all of Japan [73] Assignee: Japan Synthetic Rubber Co., Ltd.,

Tokyo, Japan [22-] Filed: March 11, 1970 [21] Appl. No.: 18,722

[30] Foreign Application Priority Data March 14,1969 Japan ..44/9292 [451 Feb. 20, 1973 UY, 67 UA, 79.7, 80.3 R, 80.3 N, 80 C, 85.5 M, 86.1, 80.8, 80.81, 86.3; 252/429 C, 431

R, 431 N, 431 P [56] References Cited UNITED STATES PATENTS 3,432,513 3/1969 Miller et a1. ..260/93.7 3,457,244 7/1969 Fukuda et al..... ..260/80.78

OTHER PUBLICATIONS Razuvayev et al., Polymerization of Vinylchloride in the Presence of the System Alkylaluminium-Alkylhalide, Polymerscience, U.S.S.R. 1965, 597-604.

Primary Examiner-James A. Seidleck Assistant Examiner-John Kight, lll Attorney-Ward, McElhannon, Brooks & Fitzpatrick [5 7 ABSTRACT A catalyst comprising an organoaluminum compound,

an organic halogen compound containing labile halogen atom, and a compound of metal of Groups IV B-Vll B or Group VIII of Demings Periodic table isuseful for copolymerizing conjugated dienes, conjugated heterodienes and, if desired, monoolfins to produce an alternate copolymer.

10 Claims, N0 Drawings PROCESS FOR PREPARING COPOLYMERS This invention relates to a process for the preparation of copolymers, in particular, alternate copolymers of conjugated diene with conjugated heterodienes along or'together with monoolefins.

By conjugated heterodiene is meant an organic compound containing two conjugated multiple bonds one of which is between a carbon atom and a nonmetallic atom other than carbon, especially 0, S and N.

Heretofore, free radical polymerization with various peroxides and other initiators has been commercially carried out for copolymerizing conjugated dienes with conjugated heterodienes, either alone or with monoolefins. However, such processes have not been successful in producing significant alternation in the repeating monomer residues. As a result the full potential of copolymerization in this field has not previously been tested.

Japanese Patent Publication No. 10996/1966 and Japanese Patent Publication No. l5984/l968 disclose a process for preparing alternate copolymer of monoolefins with conjugated heterodienes in the presence of organoaluminum halides. However, the combination of monomers used in this invention are not disclosed. When conjugated dienes and conjugated heterodienes are copolymerized in the'presence of an organoaluminum halide, the copolymer is either not formed at all or the yield is so low that commercial production by this method is not feasible.

The present inventors have previously proposed a process for preparing effectively a copolymer which comprises reacting a conjugated diene with a conjugated heterodiene and, if desired, additionally an olefin in the presence of organoaluminum compounds and organic halogen compounds containing a labile halogen atom.

As the result of further research, the present inventors have found that addition of a compound of metal of Groups IVB-VIIB or Group VIII of Demings Periodic table to a catalyst system of organoaluminum compounds and organic halogen compounds improves remarkably polymerization activity of the latter catalyst system and this new ternary catalyst system can give copolymers of higher degree of alternation and of excellent quality.

According to one aspect of the present invention there is provided a process for preparing a binary copolymer described hereafter which comprises reacting two monomers selected from the group consisting of conjugated diene (D) hereafter defined and conjugated heterodiene (H) hereafter defined, in the presence of catalyst components A (organo-aluminum compound), B (organic halogen compound containing a labile halogen atom) and C (compound of metal of Groups IVB-VIIB or VIII of Demings Periodic table).

According to another aspect of the invention there is provided a process for preparing a multicomponent copolymer which is described hereafter and which comprises reacting at least three monomers selected from at least one conjugated diene (D), at least one conjugated heterodiene (H), and mono-olefin or derivative thereof hereafter defined which optionally can be employed in the presence of catalyst components A, B and C.

CATALYST COMPONENT A This is an organoaluminum compound of the'formula:

AI R R R where R and R are, similar or dissimilar, selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl and alkoxy; and R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and alkoxy. The alkyl group in the formula is preferably that containing one to eight carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, and octyl. The cycloalkyl group may be, for example, cyclohexyl. The aryl group may be, for example, phenyl or tolyl. The aralkyl group may be, for example, benzyl. The alkoxy may be, for example, methoxy, ethoxy, propoxy, isopropoxy or butoxy.

As representative examples of the organoaluminum compound (catalyst component A), there may be mentioned trim'ethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, triphenylaluminum, triisopropoxyaluminum, diethyluluminum cthoxide,

diethylaluminum hydride. and diisobutylaluminumv hydride.

CATALYST COMPONENT B This is an organic halogen compound containing a labile halogen atom of the formula:

Q! Kai- 3 where X is halogen; Q is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl; Q and Q are, similar or dissimilar, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, aralkyl, nitrile, OR", SR NR R, CONR R,

-CZ"R", and CR" n u where R", R R R, R R and R are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and aralkyl, Z and Z are, similar or dissimilar, selected from the group consisting of oxygen and sulfur, R is selected from the group consisting of halogen, hydrogen, alkyl, cyclalkyl, aryl and aralkyl. Further, Q and Q may be, similar or dissimilar, selected from the group consisting of substituted alkyl substituted alkenyl, substituted aryl and substituted aralkyl and the substituent being selected from the group consisting of halogen, nitrile, OR SR12 NRI3RI4, CONRI5RIG -CZ"R and CR" lt Z11 where R, R R R, R, R", R" and R areas defined above.

As representative examples of catalyst component B, there may be mentioned halogenated hydrocarbons, halogenated organic acids, halogenated organic acid esters, halogenated aldehydes, halogenated alcohols, halogenated ethers, halogenated nitriles, halogenated acid halides, and halogenated acid amides. As

halogenated hydrocarbons, there are preferably used carbon tetrachloride, chloroform, tert-butyl chloride,

allyl chloride 3-chloro 2-m ethylpropene-l lchlorobutene-Z, l,4-dichlorobutene-2, benzyl chloride,

benzylidene chloride, and bis(chloromethyl) benzene. As halogenated organic acids, there are preferably used trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, tribromoacetic acid, and trifluoroacetic acid. As halogenated organic acid esters, there are preferably used ethyl trichloroacetate,

ethyl tribromoacetate, and ethyl trifluoroacetate. As

halogenated aldehydes, there are preferably used chloral and bromal. As halogenated alcohol, 2,2,2- trichloroethanol is preferably used. As halogenated ether, 2,2,2-trichlorodiethyl ether is preferably used.

As halogenated nitrile, trichloroacetonitrile is preferably used. As halogenated acid halide, trichloroacetyl chloride is preferably used. And as halogenated acid amide, trichloroacetamide is preferably used.

CATALYST COMPONENT C The catalyst component C is a compound of metal of Groups lVB-VllB or Group VIII of Demings Periodic table.

As metal of the Group lVB, titanium and zirconium are preferable. As metal of the Group VB, vanadium is preferable. As metal of the Group VIB, chromium, molybdenum and tungsten are preferable. As metal of the Group VllB, manganese is preferable. As metal of Group Vlll, iron, cobalt, nickel, ruthenium, rhodiumv and palladium are preferable.

As catalyst component C, inorganic compounds, organic compounds and complex compounds of those metals are preferably used.

As representative examples of the metal compounds, there may be mentioned halides, sulfates, nitrates, carbonates, phosphates, cyanides, thiocyanides, sulfides, hydroxides, oxides, oxyhalides, alkoxides, acid esters and organic acid salts of the metals, and complex compounds having as ligand phosphine, phosphite, carbonyl, isonitrile, dipyridyl, vinyl compound, cyclopentadienyl, 1r-allyl, acetylacetone, and acetoacetic acid ester. Further, concrete examples of these metal compounds are: TiCl Ti(-OC,H TiCl(C H TiCl (OC H 3,( 4 9)1 t s v zh, s 1 =)3, 5 )2, VC],, VOCl VO(OC H VO(OC,H V0(C H O 2s,y toqit m( MQQHQHYC QQHW 'Qb Cr(C fi-;( M0615, V M002 (C5H102)2, MnCl Ml'l(C5H702)2, MH(C5H7Oz)3, FCClg, F(OC4H9)3, FC(C5H7O2)3, Fe(octoate), Fe(stearate), Fe(C5H5) CoCl Co(C,,H O NiCl, and Ni(C H-,0

By combining the catalyst component C with the catalyst components A and B, polymerization activity of the catalyst is remarkably enhanced so that the polymerization temperature and the amount of catalyst to be used are lowered as compared with the binary catalyst consisting of the catalyst component A and the catalyst component B. Furthermore, the new ternary catalyst system can give copolymers of higher degree of alternation and of excellent quality.

The conjugated dienes (D) used in' this invention are preferably those having four to 12 carbon atoms which may be of straight chain, branched chain and ring form. Representative conjugated dienes are straight chain conjugated dienes such as butadiene, pentadiene, hex adiene, heptadiene, octadiene and the like; branched chain conjugated dienes such as isoprene, 2-ethylbutadiene, Z-tert-butylbutadiene, 3-methylheptatriene-l 4, 6 and the like; and cyclic conjugated dienes such as cyclohexadiene, cyclopentadiene and the like, and substituted conjugated dienes such as chloroprene, 2,3- dichlorobutadiene and the like. Particularly preferred are butadiene, isoprene, pentadiene and chloroprene.

The conjugated heterodienes (H) used inthis invention may include those represented by the following formulas:

R, R, R, and R are similar or dissimilar and are selected from the group consisting of hydrogen, halogen, alkyl, aryl, aralkyl, nitrile, -COOR (where R is selected from, the group consisting of hydrogen, alkyl, cycloalkyl, aryl or aralkyl) and hydrocarbon residues having a substituent selected from the group consisting of halogen and COOR where R is as defined above; Y is selected from the group consisting of halogen, R OR -NRR and SR where R R R, R and R are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and aralkyi; arrdZ isselected from the group consisting of oxygen and sulfur. Further, when the conjugated heterodienes of the above formulas have a carboxyl group, the corresponding acid anhydride is also within the scope of the conjugated heterodienes used in this invention.

Representative examples of the conjugated heterodienes (H) are unsaturated carboxylic acids, unsaturated carboxylic acid esters, unsaturated aldehydes, unsaturated acid halides, unsaturated acid amides, unsaturated keytones, unsaturated thiolic acids, unsaturated thiolic acid esters, unsaturated thionic acids, unsaturated thionic acid esters, and unsaturated nitrile compounds.

Among the above mentioned compounds the following compounds are employed preferably: unsaturated carboxylic acid acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride; unsaturated carboxylic acid ester methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methyl crotonate, methyl cinnamate, monomethyl maleate, dimethyl maleate, monomethyl fumarate, dimethyl fumarate, ethyl itaconate, and diethyl itaconate; unsaturated aldehyde acrolein, methacrolein; unsaturated acid halide acryloyl chloride; unsaturated acid amide acrylamide, and methacrylamide; unsaturated ketone methyl vinyl ketone, and methyl isopropenyl ketone; unsaturated nitrile compound acrylonitrile, methacrylonitrile, chloroacrylonitrile,

and vinylidene cyanide.

Particularly preferable compounds are acrylonitrile,

methacrylonitrile, methyl acrylate, ethyl acrylate, butyl.

acrylate, methyl methacrylate, ethyl methacrylate, butylmethacrylate, maleic anhydride, and dimethyl fumarate.

The monoolefins used in this invention together with the above-mentioned conjugated dienes (D) and conjugated heterodienes (H) are those containing two to 16 carbon atoms.

Representative monoolefins are aliphatic straight chain olefins such as ethylene, propylene, butene-l butene-2, isobutene, pentene-l, pentene-2, 2-methylbutene-l, 3-methyl-butene-l, 2-methylbutene-2, hexenel, hexene-2, 2-methyl-pentene-l, dodecene-l and the like; aliphatic cyclic (including bridge or aromatic fused ring) olefins such as cyclobutene, cyclopentene, cyclooctene, norbomene, indene and the like; aromatic vinyl compounds such as styrene, a-methyl-styrene, vinyl toluene, vinyl naphthalene, N-vinylcarbazole and the like; vinyl ester compounds such as vinyl acetate, vinyl propionate and the like; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like; and halogen substituted olefins such as vinyl chloride, vinylidene chloride and the like.

The catalyst components may be used in an optional ratio with respect to the monomers. In general it is preferable to use 0.0001 to 10 moles of catalyst (based on catalyst component A) per one mole of a conjugated heterodiene, particularly preferred is a ratio of 0.0015 to 5 moles catalyst per mole of conjugated heterodiene.

The ratio of catalyst component B to catalyst component A may be optionally selected through the preferable ratio is varied depending upon the type of catalyst component C. The ratio is preferably 0.05 to 20 moles (particularly 0.1 to moles) of catalyst com-' ponent B per mole of catalyst component A. Further, the ratio of catalyst component C to catalyst component A is generally 0.0001-10 moles (component C) per 1 mole (component A), preferred with 0.0001-1 mole per 1 mole.

The process ofthis invention may be effected in the presence or absence of solvent. As the solvent, hydrocarbon solvents or halogenated hydrocarbon solvents may be used. As hydrocarbon solvents, there may be mentioned, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like;

aromatic hydrocarbons such as benzene, toluene and the like; and alicyclic hydrocarbons such as cyclohexane and the like. As halogenated hydrocarbons, there may be mentioned, for example, solvents inert to catalyst component A such as methylene chloride, tetrachloroethylene, chlorobenzene, dichlorobenzene and the like.

These solvents prevent an undue increase in viscosity during polymerization and are effective to carry out smooth polymerization. It is also possible to use an excess of a monomer itself as a solvent.

The polymerization temperature is not critical but it is preferable to effect the polymerization within a temperature range of -80C to 150C.

Neither is the reaction pressure critical, to the extent that the reaction mixture can be retained in a liquid state under pressure if necessary or desired.

The polymerization reaction is preferably carried out in .an inert gas atmosphere. After the completion of the polymerization reaction, the product may be recovered by conventional methods.

Further, by the present invention there is provided an alternate copolymer comprising at least two residues of monomers selected from the group consisting of conjugated diene (D) and conjugated heterodiene (H), (The residues of the respective monomers being designated D and H) wherein any one of residue of D and H is linked to the other type of residue H and D, respectively.

Furthermore, by the present invention there is provided an alternate copolymer comprising at least one residue of conjugated dienes (D) at least one residue of conjugated heterodienes (H) and at least one residue of monoolefins or derivatives thereof (0) in which the repeating unit comprises two types of residues, one type being residue H and the other type being residue or 0, wherein a residue of any one of the types is linked to a residue of the other type. The invention includes both random sequences and specific chain sequences such as The combination of monomers employed in this invention is a combination of two or more members selected from the class consisting of conjugated dienes (D) and conjugated heterodienes (H) or a combination of monoolefins (O) and the above-mentioned combination. In other words, when a monoolefin is used at least one conjugated diene and at least one conjugated heterodiene must be combined with it.

More than one compound from any one of the three general types may be used in any one copolymer. For example the combinations of monomers reacted may include:

D,H,O,H',H,

Representative combinations are as follows:

Binary Copolymer Butadiene acrylonitrile Butadiene methyl methacrylate Butadiene methyl acrylate Butadiene acrolein Butadiene chloroprene lsoprene acrylonitrile lsoprene methyl methacrylate lsoprene methyl acrylate lsoprene acrolein Pentadiene acrylonitrile Pentadiene methyl methacrylate Pentadiene methyl acrylate Pentadiene acrolein Cyclopentadiene acrylonitrile Acrylonitrile methacrylic acid Acrylonitrile acrolein Ternary Copolymer Butadiene acrylonitrile methyl methacrylate Butadiene acrylonitrile styrene Butadiene acrylonitrile isobutene Butadiene acrylonitrile butene l Butadiene acrylonitrile acrolein Butadiene methyl methacrylate styrene Butadiene methyl methacrylate isobutene Butadiene methyl methacrylate butene 1 Butadiene isoprene acrylonitrile Butadiene isoprene methyl methacrylate Butadiene chloroprene acrylonitrile Butadiene chloroprene methacrylic acid Butadiene pentadiene acrylonitrile Butadiene pentadiene methyl methacrylate- Butadiene maleic anhydride acrylonitrile Butadiene maleic anhydride methacrylonitrile Butadiene maleic anhydride butene l Butadiene maleic anhydride isobutene lsoprene acrylonitrile methyl methacrylate isoprene acrylonitrile styrene lsoprene acrylonitrile isobutene lsoprene methyl methacrylate styrene isoprene methyl methacrylate isobutene isoprene maleic anhydride acrylonitrile isoprene maleic anhydride methacrylonitrile lsoprene maleic anhydride butene l isoprene maleic anyydride isobutene According to the process of this invention, alternate copolymers can be obtained. When butadiene and acrylonitrile are copolymerized in the presence of the catalyst system of this invention, the monomer reactivity ratios thereof are low (for example, when the polymerization is effected in heptane at 40C in the presence of a catalyst comprising triethylaluminumtrichloroacetic acid-ferric butoxide, 7 is 0.04, y is 0.085 and therefore, y X 7,, 0.0034 where y is monomer reactivity ratio of acrylonitrile and, 7 is of butadiene,) and thereby a highly alternate copolymer can be obtained. The mechanism is believed to depend on the fact that a monomer coordinated to the catalyst reacts sparingly with the same kind of monomer, but easily reacts with a different one of the monomer types and the reaction is accelerated by the addition of the other types of monomer. However, this invention should not be understood as being restricted by the theoretical mechanism. The state of bonding of the monomer units in the copolymer produced by the process of this invention varies depending upon the combination of catalyst components, the combination of monomers, and the polymerization conditions. As shown in the Examples below, some copolymer obtained by the process of this invention contain the monomer units-in an alternate bonding state of almost 1:1 or at least in a highly alternate bonding state, re-

' ga'rdless of the ratio of charged monomers and the polymer yield.

Even when the ratio of monomers used in the original feed in not 1:1 in the case of some binary copolymer, the ratio of monomer units in the resulting copolymer is almost 1:1, and in a similar way, some ternary copolymer containing a constant ratio of monomer units can be obtained. Excess of conjugated heterodiene monomer charged to the copolymerization system will in general act simply as solvent and can be used for this purpose. The effect of the excess monomer is in general to raise catalyst activity, increase the molecular weight of the resulting copolymer, and to form the alternate copolymer more effectively.

The copolymers obtained by the process of this invention are novel and a feature of this invention is to provide such novelcopolymers.

. The novel alternate copolymers obtained according to this invention can be of high molecular weight, and

their properties range from rubber-like to plastic depending upon the combination of monomers used. The preferred novel copolymers have particularly good strength and can be used in various fields where conventional rubber and plastics have been used. Furthermore, it is possible to apply the novel copolymers to new fields where their particular characteristics can be effectively utilized.

The following examples are given for illustrating the present invention,-but not for limiting the scope 'of this invention.

EXAMPLES 1-103 AND REFERENCE EXAMPLES 1-12 A ml. ampoule is dried sufficiently, and nitrogen gas is substituted several timesThen, according to the formulation of Table below, there are added to the ampoule a dried solvent at 10C a molar solution of respective organic-halogen compounds as catalyst component B in a solvent, a 0.1 molar solution of a transition metal compound as catalyst component C in a solvent, followed by agitating for 5 minutes. Then, there is further added a molar solution of respective organoaluminum compound as catalyst component A in a solvent, followed by agitating further for 15 minutes, and after agitation conjugated heterodiene compound and conjugated diene compound, and if desired olefin are added. Immediately, the ampoule is sealed. All the procedures as above are carried out in a nitrogen atmosphere.

The ampoule is rotated in a rotating polymerization vessel to effect copolymerization. After a determined time, the ampoule is opened and then a small amount of phenyl-fl-naphthylamine is added thereto and mixed thoroughly to stop the copolymerization. The reaction mixture is poured into a hydrochloric acid-methanol solution containing antioxidant to decompose and dissolve the catalyst and simultaneously the resulting copolymer is precipitated. The precipitated copolymer is separated and washed several times with methanol containing antioxidant, and dried at 40C under reduced pressure overnight. The result is shown table below.

The symbols in the following table are defined as below: i

Et; ethyl Bu; butyl AcAc; acetyl acetone AN; acrylonitrile BD; butadiene Hex; hexyl TCA; trichloroacetic acid MMA; methyl methacrylate lP; isoprene CP; chloroprene MAN; methacrylonitrile MAn; maleic anhydride ST; styrene Oct; octenic acid Ste; stearic acid IB; isobutylene What is claimed is: l. A process for preparing conjugated compounds polymers which comprises contacting a monomeric AI R R R where R and R are, similar or dissimilar, selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl and alkoxy and R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and alkoxy, component B selected from the group consisting of halogenated organic acids, halogenated organic acid esters, halogenated aldehydes, halogenated alcohols, halogenated ethers, halogenated nitriles, halogenated acid halides, and halogenated acid amides, and component C selected from the group consisting of halides, sulfates, nitrates, carbonates, phosphates, cyanides, thiocyanides, sulfides, hydroxides, oxides, oxyhalides, alkoxides, acid esters, organic acid salts, complex compounds having as ligand phosphine, phosphite, carbonyl, isonitrile, dipyridyl, vinyl compound, cyclopentadienyl, rr-allyl, acetylacetone, and

- acetoacetic acid ester of iron, cobalt, nickel, ruthenium, rhodium, and palladium.

2. A process as claimed inclaim l in which the component B is the compound having a trihalomethyl group.

3. A process for preparing conjugated compounds polymers which comprises contacting a monomeric material selected from the group consisting of (l) a mixture of at least two conjugated compounds selected from conjugated dienes (D) and conjugated heterodienes (H) and 2) a mixture of at least one conjugated diene (D), at least one conjugated heterodiene (H) and at least one monoolefin or derivative thereof 7 (O) with a catalyst comprising component A of the formula:

where R and R are, similar or dissimilar, selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl and alkoxy and R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and alkoxy, component B selected from the group consisting of trichloroacetic acid, dichloroacetic acid,

monochloroacetic acid, tribromoacetic acid trifluoroacetic acid, ethyl trichloroacetate ethyl tribromoacetate, ethyl trifluoro-acetate chloral,

bromal, 2,2,2-trichloroethanol, 2,2,2-trichlorodiethyl ether, trichloroacetonitrile, trichloroacetyl chloride, and trichloroacetamide, and component C selected from the group consisting of FeCl:,, Fe(OC.,H,,) F6(C H Oz)a, Fe(octoate), Fe(stearate), Fe( C5H )2, COCl CO(C5H72)3, Niclz, and Ni(C5H-,O1)2- 4. A process as claimed in claim 1 wherein the mixture of at least two conjugated compounds is a combination of a conjugated diene and a conjugated heterodiene.

5. A process as claimed in claim 1 wherein the conjugated dienes (D) are conjugated dienes having four to 12 carbon atoms selected from straight chain, branched chain and ring form.

6. A process as claimed in claim 5 wherein the conjugated dienes are selected from the group consisting of butadiene, pentadiene, hexadiene, heptadiene, octadiene, isoprene, 2-ethylbutadiene, 2-tert-butylbutadiene, 3-methyl-heptatriene-l, 4, 6, cyclohexadiene, cyclopentadiene, chloroprene and 2,3-dichlorobutadiene.

7. A process as claimed in claim 1 wherein the conjugated heterodienes are selected from the group consisting of a compound having the formula:

H= Ll- =z and a compound having the formula:

where R, R, R and R are, similar or dissimilar, selected from the group consisting of hydrogen, halogen, alkyl, aryl, aralkyl, nitrile, COOR (where R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and aralkyl) and hydrocarbon residue having a substituent selected from the group consisting of halogen and -COOR where R is as defined above: Y is selected from the group consisting of halogen, R OR NRR and -SR" where R, R, R, R and R are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and aralkyl; and Z is selected from the group consisting of oxygen and sulfur; and further when the conjugated heterodienes of the above formulas have a carboxyl group, the corresponding anhydride is also included.

8. A process as claimed in claim 7 wherein the conjugated heterodienes are selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, fuma ric acid, itaconic acid, maleic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methyl crotonate, methyl cinnamate, monoethyl maleate, dimethyl maleate, monoethyl fumarate, dimethyl fumarate, ethyl itaconate, diethyl itaconate, acrolein, methacrolein, acryloyl chloride, acrylamide, methacrylamide, methyl vinyl ketone, methyl isopropyl ketone, acrylonitrile, methac'rylo-nitrile, chloroacrylonitrile and vinylidene cyanide.

9. A process as claimed in claim 1 wherein the monoolefin or derivative thereof contains from two to 16 carbon atoms.

10. A process as claimed in claim 9 wherein the monoolefin or derivative thereof containing two to 16 carbon atoms is selected from the group consisting of ethylene, propylene, butene-l, butene-2, isobutene, pentene-l, pentene-2, 2-methylbutenel, 3-methylbutene-l, 2-methyl-butene-2, hexene-l, hexene-2, 2- methylpentene-l, dodecene-l, cyclobutene, cyclopentene, cyclooctene,norbornene, indene, styrene, a 

1. A process for preparing conjugated compounds polymers which comprises contacting a monomeric material selected from the group consisting of (1) a mixture of at least two conjugated compounds selected from conjugated dienes (D) and conjugated heterodienes (H) and (2) a mixture of at least one conjugated diene (D),at least one conjugated heterodiene (H) and at least one monoolefin or derivative thereof (O) with a catalyst comprising component A of the formula: Al R1 R2 R3 where R1 and R2 are, similar or dissimilar, selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl and alkoxy and R3 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and alkoxy, component B selected from the group consisting of halogenated organic acids, halogenated organic acid esters, halogenated aldehydes, halogenated alcohols, halogenated ethers, halogenated nitriles, halogenated acid halides, and halogenated acid amides, and component C selected from the group consisting of halides, sulfates, nitrates, carbonates, phosphates, cyanides, thiocyanides, sulfides, hydroxides, oxides, oxyhalides, alkoxides, acid esters, organic acid salts, complex compounds having as ligand phosphine, phosphite, carbonyl, isonitrile, dipyridyl, vinyl compound, cyclopentadienyl, pi -allyl, acetylacetone, and acetoacetic acid ester of iron, cobalt, nickel, ruthenium, rhodium, and palladium.
 2. A process as claimed in claim 1 in which the component B is the compound having a trihalomethyl group.
 3. A process for preparing conjugated compounds polymers which comprises contacting a monomeric material selected from the group consisting of (1) a mixture of at least two conjugated compounds selected from conjugated dienes (D) and conjugated heterodienes (H) and (2) a mixture of at least one conjugated diene (D), at least one conjugated heterodiene (H) and at least one monoolefin or derivative thereof (O) with a catalyst comprising component A of the formula: Al R1 R2 R3 where R1 and R2 are, similar or dissimilar, selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl and alkoxy and R3 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and alkoxy, component B selected from the group consisting of trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, tribromoacetic acid, trifluoroacetic acid, ethyl trichloroacetate, ethyl tribromoacetate, ethyl trifluoro-acetate, chloral, bromal, 2,2,2-trichloroethanol, 2,2, 2-trichlorodiethyl ether, trichloroacetonitrile, trichloroacetyl chloride, and trichloroacetamide, and component C selected from the group consisting of FeCl3, Fe(OC4H9)3, Fe(C5H7O2)3, Fe(octoate), Fe(stearate), Fe(C5H5)2, CoCl2, Co(C5H72)3, NiCl2, and Ni(C5H7O2)2.
 4. A process as claimed in claim 1 wherein the mixture of at least two conjugated compounds is a combination of a conjugated diene and a conjugated heterodiene.
 5. A process as claimed in claim 1 wherein the conjugated dienes (D) are conjugated dienes having four to 12 carbon atoms selected from straight chain, branched chain and ring form.
 6. A process as claimed in claim 5 wherein the conjugated dienes are selected from the group consisting of butadiene, pentadiene, hexadiene, heptadiene, octadiene, isoprene, 2-ethylbutadiene, 2-tert-butylbutadiene, 3-methyl-heptatriene-1, 4, 6, cyclohexadiene, cyclopentadiene, chloroprene and 2,3-dichlorobutadiene.
 7. A process as claimed in claim 1 wherein the conjugated heterodienes are selected from the group consisting of a compound having the formula: and a compound having the formula: where R4, R5, R6 and R7 are, similar or dissimilar, selected from the group consisting of hydrogen, halogen, alkyl, aryl, aralkyl, nitrile, -COOR21 (where R21 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and aralkyl) and hydrocarbon residue having a substituent selected from the group consisting of halogen and -COOR21 where R21 is as defined above: Y is selected from the group consisting of halogen, -R22, -OR23, -NR24R25 and -SR26 where R22, R23, R24, R25 and R26 are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and aralkyl; and Z is selected from the group consisting of oxygen and sulfur; and further when the conjugated heterodienes of the above formulas have a carboxyl group, the corresponding anhydride is also included.
 8. A process as claimed in claim 7 wherein the conjugated heterodienes are selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methyl crotonate, methyl cinnamate, monoethyl maleate, dimethyl maleate, monoethyl fumarate, dimethyl fumarate, ethyl itaconate, diethyl itaconate, acrolein, methacrolein, acryloyl chloride, acrylamide, methacrylamide, methyl vinyl ketone, methyl isopropyl ketone, acrylonitrile, methacrylo-nitrile, chloroacrylonitrile and vinylidene cyanide.
 9. A process as claimed in claim 1 wherein the monoolefin or derivative thereof contains from two to 16 carbon atoms. 